CN1709570A - Method for preparing catalyst for refining of crude terephthalic acid - Google Patents
Method for preparing catalyst for refining of crude terephthalic acid Download PDFInfo
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- CN1709570A CN1709570A CN 200410025266 CN200410025266A CN1709570A CN 1709570 A CN1709570 A CN 1709570A CN 200410025266 CN200410025266 CN 200410025266 CN 200410025266 A CN200410025266 A CN 200410025266A CN 1709570 A CN1709570 A CN 1709570A
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Abstract
This is a kind of producing method of catalyst used for refining coarse terephthalic acid (CTA). The catalyst makes grains or molding active carbon as carrier, the content of loading active component metal Pd is 0.2 - 4wt%. It orderly includes: have acid wash to carrier active carbon; wash carrier active carbon with water to neutral; have soakage with watery solution containing nitrite ion to carrier active carbon; dry carrier active carbon to get rid of water; prepare Pd solution with water-soluble Pd compound, a kind of complexing agent and water to infuse or insufflate the carrier active carbon; the content of Pd compound in the Pd solution counted by Pd is 15 - 20wt%; the mol proportion of complexing agent and Pd is (0.01 - 1) : 1, the complexing agent is got from anyone of 8-hydroxyquinoline, 2, 3, 4-trihydroxyl-4-sulfonic azobenzol, o-phenanthroline, o-Aminophenol, o-hydroxybenzoic sodium or o-hydroxybenzaldehyde oxime; after aginged, have deoxidizing treatment with reducing agent to get activator products.
Description
Technical field
The present invention relates to a kind of preparation method who is used for the supported palladium/carbon catalyst of hydrogenation reaction, particularly be used for making with extra care the preparation method of the supported palladium/carbon catalyst of crude terephthalic acid by selective hydrogenation.
Background technology
Supported palladium/carbon catalyst is mainly used in the selective hydrogenation of unsaturated compounds, be particularly useful for the refining of crude terephthalic acid, in the crude terephthalic acid impurity such as carboxyl benzaldehyde (be called for short 4-CBA) are changed into other compound after by hydrogenation, separate purification with regard to available crystalline method subsequently.Because palladium/carbon catalyst usually adopts single active constituent, in the prior art its improvement research is concentrated on always the structure and the distribution situation of metal Pd on carrier of carrier, and this can produce very big influence to the performance of catalyzer really.
Because terephthalic acid hydrofining reaction process is a first order reaction, speed of response is fast, react the inside that reactant is difficult to be penetrated into granules of catalyst in the reaction process, this just makes the active ingredient of granule interior not play a role, for the consideration that makes full use of precious metal, usually palladium/carbon catalyst is made eggshell type, promptly allows the basic load of active constituent precious metal in the surface of carrier.
Because hydrogenation reaction is to carry out on the surface of metal Pd, therefore usually for the identical catalyzer of metal Pd charge capacity, the dispersity of its metal Pd is higher, or the content of crystallite of the metal Pd of load is higher in the catalyzer, activity of such catalysts is just higher, and work-ing life is also longer.
If directly will contain Pd compound (as chlorine palladium acid sodium or Palladous chloride) loads on the gac, activated carbon surface can the very thin glossiness metal Pd layer of very fast appearance, this mainly is because activated carbon surface contains just like reduction groups such as aldehyde radical, unbound electrons, very easily make the Pd ion be reduced into the non-valent metal Pd, thereby the dispersity of metal Pd is very low in the catalyzer that causes making.According to experience in the past, the Pd ion that will contain before the operation in the steeping fluid of Pd compound in reduction is transformed into the effect that insoluble compound can be obtained, as at room temperature the water-soluble cpds hydrolysis of Pd being changed into insoluble Pd (OH)
2Or PdOH
2Load on again behind the O on the gac,, can prevent migration and the grain growth of Pd so subsequently with the reduction of reductive agents such as formaldehyde, sodium formiate, glucose, formic acid or hydrogen.As U.S. Pat 3,138,560 are introduced, and it adds hydrogen peroxide in steeping fluid makes the water-soluble cpds hydrolysis of Pd generate insoluble compound.But because hydrogen peroxide itself also has oxidisability, it can be with the activated carbon surface radical oxidation, thereby will change the Surface Physical Chemistry character of carrier, promptly change the surface group structure of carrier, this has stronger uncertain negative impact, can damage other performance of catalyzer, as carrying palladium intensity, catalyst life, selectivity etc.U.S. Pat 4; 476; the steeping fluid that contains the Pd compound is prepared in 242 propositions with organic solvents such as methyl alcohol or pyridines; it is said that this is also very effective to the migration and the grain growth that prevent Pd; but production process use methyl alcohol or pyridine are this in human body harmful's organic compound, all are disadvantageous from ring environment protection or labour protection.In addition, there is patent report chlorine palladium acid solution to be transformed into the palladium glue by adjusting pH value, allegedly can prevent that also the reduction group of activated carbon surface directly is reduced into the non-valent metal Pd with the Pd ion, but glue stability is bad, be difficult to uniform distribution on carrier active carbon, this can influence the dispersiveness of Pd equally.
Summary of the invention
The invention provides a kind of Preparation of catalysts method that is used for refining crude terephthalic acid, its technical problem to be solved is to make that metal Pd has higher dispersity and content of crystallite in the catalyzer that makes, and can overcome existing with the existing defective of class methods simultaneously again.
Below be the technical scheme that the present invention solves the problems of the technologies described above:
A kind of Preparation of catalysts method that is used for refining crude terephthalic acid, catalyzer is a carrier with particle or pressed active carbon, supported active component metal Pd.The content of metal Pd is 0.2～4wt% in the catalyzer, and this preparation method may further comprise the steps successively:
1) carrier active carbon carries out pickling, and the acid concentration of pickle solution is 0.1～5N, and a kind of in hydrochloric acid, nitric acid or the phosphoric acid taken from acid;
2) carrier active carbon is washed with water to neutrality;
3) carrier active carbon is with halogen-containing ionic solution immersion, and the halogen ion concentration of infiltrate is 0.01～0.5N, and the infiltrate consumption is 0.1～3.0 times of gac saturated extent of adsorption, and infiltrating time is 2～24 hours;
4) the drying support gac is removed moisture;
5) be mixed with Pd solution with the water-soluble Pd of containing compound and a kind of complexing agent and water, with Pd solution impregnation or sprinkling carrier active carbon, make and contain that Pd is compound loaded to obtain catalyst precursor in gac, the content that contains the Pd compound in the Pd solution is counted 15～20wt% with Pd, the mol ratio of complexing agent and Pd is (0.01～1): 1, complexing agent is taken from oxine, 2,3, any in 4-trihydroxy--4-sulfonic acid nitrogen benzide, phenanthroline, Ortho-Aminophenol, salicylic acid sodium or the salicylaldhyde oxime;
6) catalyst precursor reduces processing with reductive agent after aging, makes divalence Pd in the Pd compound be reduced to metal Pd and promptly gets catalyst prod.
Halide-ions described in the above-mentioned steps 3 is preferably Br
-1Or I
-1Described halide-ions is preferably from alkali-metal halogenide, and wherein the halogenide with potassium is the best.
Above-mentioned steps 5 described complexing agents are preferably oxine, 2,3,4-trihydroxy--4-sulfonic acid nitrogen benzide or phenanthroline; And the mol ratio of complexing agent and Pd is preferably (0.05～0.6): 1; The described Pd of containing compound can be taken from any in the title complex of the subsalt of halogenide, acetate, nitrate, the acid of chlorine palladium, the acid of chlorine palladium of Pd or palladium ammonia usually, is the best with acid of chlorine palladium or palladium wherein.
Above-mentioned steps 6 described reductive agents can be taken from any in formic acid, sodium formiate, formaldehyde, hydrazine hydrate, glucose or the hydrogen usually, wherein are best with the sodium formiate.
In the present invention, remove and to have added complexing agent when having increased carrier active carbon with the preparation of halogen-containing this step of ionic solution immersion and Pd solution, other parts are then basic identical with existing general palladium/carbon catalyst preparation method, and these preparation process are that those skilled in the art are known, can be usually:
Select suitable gac for use, remove the dust and surface porosity part of carbon surface absorption after, in the washing still, carry out pickling, after the pickling with deionized water wash to neutral.
Carrier active carbon is with halogen-containing ionic solution immersion, and drying is removed moisture then.
Get and contain the Pd compound and required complexing agent water is mixed with Pd solution, adopt methods such as dipping or sprinkling to make then and contain the compound loaded catalyst precursor that on carrier, makes of Pd, then with catalyst precursor in air aging 1～24 hour.
Catalyst precursor after aging is handled with the reductive agent reduction, and reduction temperature is 0～2 00 ℃, and the best is 50～120 ℃.The consumption of reductive agent depends on the dosage of active constituent Pd, is generally normal 1～10 times of reduction reaction, is preferably 2～5 times, and the recovery time is 1～10 hour, and the best is 1～4 hour.
With respect to prior art, improvements one of the present invention are to have increased step 3 wherein, and carrier active carbon with halogen-containing ionic solution immersion, makes halide-ions be adsorbed in activated carbon surface after pickling.Because halide-ions can be distributed in activated carbon surface very equably, and halide-ions and palladium and activated carbon surface all have affinity interaction power preferably, this has just increased the grappling effect of activated carbon surface to palladium, thereby the migratory movement that can reduce palladium is to stop or to delay the grain growth of palladium metal.
The 2nd, when the preparation of Pd solution, added complexing agent, complexing agent can produce stronger interaction and generate a kind of complex compound with Pd, so can reduce the redox-potential of Pd, when Pd loads on the gac, the Pd ion just can not reduced by the activated carbon surface group, thereby the Pd ion can be distributed in activated carbon surface very equably.
Compared with prior art, the invention has the advantages that metal Pd has higher dispersity in the catalyzer that makes, content of crystallite is higher, on use properties, show active high, long service life, and the step that increases in the preparation process is very simple, the raw material that adopts is easy to environmental protection treatment, and the method that adopts can not produce any negative impact to catalyzer.
Below will the invention will be further described by specific embodiment, just as described above, method for preparing catalyst provided by the invention mainly comprises six steps, wherein except that step 3 and step 5, other parts and prior art are basic identical, so embodiment will pay attention to giving an example of step 3 and step 5.
In an embodiment:
The measuring method of content of crystallite:
Record the palladium metal particle diameter by X-fluorescence spectrophotometer and x-ray diffractometer (XRD), calculate content of crystallite by following formula then:
The activity rating of catalyst condition:
Catalyst consumption: 2.0g
Thick p-Xylol amount: 30.0g
4-CBA amount: 1.0g
Reaction pressure: 70 kilograms
Hydrogen partial pressure: 5.0 kilograms
Reaction times: 1.0 hours
Temperature of reaction: 270 ℃
Embodiment
[embodiment 1]
With 100 grams, 4～8 orders, specific surface 800～1800m
2The cocoanut active charcoal of/g washs with the nitric acid of 0.4N, and wash temperature is 80 ℃, is washed with water to neutrality then.
With Potassium Bromide and water preparation Br
-Concentration is the infiltrate of 0.01N, incipient impregnation gac 2～24 hours, and 80～120 ℃ times dry 2～8 hours are standby.
The chlorine palladium acid solution that contains palladium 15wt% of aequum is got in the preparation of Pd solution, adds deionized water to 40 milliliter, adds the acidic aqueous solution that contains oxine 5wt% of aequum more therein, and adds 60 milliliters of deionized water preparation Pd solution.Behind solution-stabilized 10～200 minutes of the Pd, above-mentioned treated gac is obtained catalyst precursor with the Pd solution impregnation after 3 hours.Aging 24 hours of catalyst precursor is mixed with reduced liquid with hydrazine hydrate 20 grams and pure water 200 grams of 5wt%, and catalyst precursor is immersed in the reduced liquid 2～4 hours, also in addition gets catalyst prod after the drying with the pure water washing to neutral then.
[embodiment 2～8]
Select for use different halogenide to prepare halogen-containing ionic infiltrate, all the other are with embodiment 1.It is 1 listed that concrete halogenide and infiltrate halogen ion concentration see Table.
[embodiment 9～31]
Select for use different to contain the Pd compound and complexing agent is prepared Pd solution, all the other are with embodiment 1.
[embodiment 32～37]
Select for use different to contain the Pd compound and complexing agent is prepared Pd solution, Pd obtains catalyst precursor with the Pd spray solution after solution-stabilized 10～200 minutes on gac, and all the other are with embodiment 1.
[comparative example]
Be washed with water to neutrality after the gac pickling, drying, gac is directly used the Pd solution impregnation then, and preparation Pd does not add complexing agent during solution, and all the other are with embodiment 1.
It is 2 listed that the concrete mol ratio that contains the content (in Pd) that contains the Pd compound in Pd compound, the Pd solution, concrete complexing agent and complexing agent and Pd that each embodiment and comparative example adopt sees Table, the content of the catalyst metal Pd that makes see Table 3 first be listed as listed.
The catalyzer that each embodiment and comparative example make carries out dispersity and content of crystallite is measured, and adopts above-mentioned activity rating of catalyst condition to carry out activity rating, and it the results are shown in Table 3.
Table 1.
| Halogenide | Halide-ions | Plain ionic concn (N) | |
| Embodiment 1 | Potassium Bromide | ????Br - | ????0.01 |
| Embodiment 2 | Potassium Bromide | ????Br - | ????0.05 |
| Embodiment 3 | Potassium Bromide | ????Bf - | ????0.20 |
| Embodiment 4 | Potassium Bromide | ????Bf - | ????0.50 |
| Embodiment 5 | Potassiumiodide | ????I - | ????0.01 |
| Embodiment 6 | Potassiumiodide | ????I - | ????0.05 |
| Embodiment 7 | Potassiumiodide | ????I - | ????0.20 |
| Embodiment 8 | Potassiumiodide | ????I - | ????0.50 |
| Embodiment 9～20 | Potassium Bromide | ????Br - | ????0.01 |
| Comparative example | ????/ | ????/ | ????/ |
Table 2.
| The Pd compound | Complexing agent | Pd content (wt%) in the solution | Complexing agent/Pd (mol ratio) | |
| Embodiment 1～8 | The acid of chlorine palladium | Oxine | ??0.51 | ??0.40 |
| Embodiment 9 | The acid of chlorine palladium | Oxine | ??0.51 | ??0.05 |
| Embodiment 10 | The acid of chlorine palladium | Oxine | ??0.51 | ??0.10 |
| Embodiment 11 | Palladium | Oxine | ??0.51 | ??1.00 |
| Embodiment 12 | The acid of chlorine palladium | 2,3,4-trihydroxy--4-sulfonic acid nitrogen benzide | ??0.51 | ??0.05 |
| Embodiment 13 | The acid of chlorine palladium | 2,3,4-trihydroxy--4-sulfonic acid nitrogen benzide | ??0.51 | ??0.10 |
| Embodiment 14 | The acid of chlorine palladium | 2,3,4-trihydroxy--4-sulfonic acid nitrogen benzide | ??0.21 | ??0.40 |
| Embodiment 15 | Palladium | 2,3,4-trihydroxy--4-sulfonic acid nitrogen benzide | ??0.51 | ??1.00 |
| Embodiment 16 | The acid of chlorine palladium | Phenanthroline | ??0.51 | ??0.05 |
| Embodiment 17 | The acid of chlorine palladium | Phenanthroline | ??0.51 | ??0.10 |
| Embodiment 18 | The acid of chlorine palladium | Phenanthroline | ??0.51 | ??0.40 |
| Embodiment 19 | Palladium | Phenanthroline | ??3.7 | ??1.00 |
| Embodiment 20 | The acid of chlorine palladium | Ortho-Aminophenol | ??0.51 | ??0.02 |
| Embodiment 21 | The acid of chlorine palladium | Ortho-Aminophenol | ??0.51 | ??0.10 |
| Embodiment 22 | The acid of chlorine palladium | Ortho-Aminophenol | ??0.51 | ??0.40 |
| Embodiment 23 | Palladium | Ortho-Aminophenol | ??0.51 | ??1.00 |
| Embodiment 24 | The acid of chlorine palladium | Salicylic acid sodium | ??0.51 | ??0.05 |
| Embodiment 25 | The acid of chlorine palladium | Salicylic acid sodium | ??0.51 | ??0.10 |
| Embodiment 26 | The acid of chlorine palladium | Salicylic acid sodium | ??0.51 | ??0.40 |
| Embodiment 27 | Palladium | Salicylic acid sodium | ??0.51 | ??1.00 |
| Embodiment 28 | The acid of chlorine palladium | The salicylaldhyde oxime | ??0.51 | ??0.05 |
| Embodiment 29 | The acid of chlorine palladium | The salicylaldhyde oxime | ??0.51 | ??0.10 |
| Embodiment 30 | The acid of chlorine palladium | The salicylaldhyde oxime | ??0.51 | ??0.40 |
| Embodiment 31 | Palladium | The salicylaldhyde oxime | ??0.51 | ??1.00 |
| Embodiment 32 | The acid of chlorine palladium | Oxine | ??0.51 | ??0.50 |
| Embodiment 33 | The acid of chlorine palladium | 2,3,4-trihydroxy--4-sulfonic acid nitrogen benzide | ??0.51 | ??0.50 |
| Embodiment 34 | The acid of chlorine palladium | Phenanthroline | ??0.51 | ??0.50 |
| Embodiment 35 | Palladium | Ortho-Aminophenol | ??0.51 | ??0.50 |
| Embodiment 36 | The acid of chlorine palladium | Salicylic acid sodium | ??0.51 | ??0.50 |
| Embodiment 37 | Palladium | The salicylaldhyde oxime | ??0.51 | ??0.50 |
| Comparative example | The acid of chlorine palladium | ??/ | ??0.51 | ??/ |
Table 3.
| Pd content (wt%) | Dispersity (%) | Content of crystallite (%) | Transformation efficiency (%) | |
| Embodiment 1 | ??0.5 | ??34 | ??89 | ??100 |
| Embodiment 2 | ??0.5 | ??33 | ??90 | ??99.9 |
| Embodiment 3 | ??0.5 | ??32 | ??88 | ??99.8 |
| Embodiment 4 | ??0.5 | ??32 | ??90 | ??99.9 |
| Embodiment 5 | ??0.5 | ??36 | ??91 | ??100 |
| Embodiment 6 | ??0.5 | ??35 | ??89 | ??100 |
| Embodiment 7 | ??0.5 | ??36 | ??93 | ??99.9 |
| Embodiment 8 | ??0.5 | ??34 | ??89 | ??100 |
| Embodiment 9 | ??0.5 | ??16 | ??78 | ??99.6 |
| Embodiment 10 | ??0.5 | ??18 | ??82 | ??99.7 |
| Embodiment 11 | ??0.5 | ??28 | ??86 | ??99.8 |
| Embodiment 12 | ??0.5 | ??17 | ??80 | ??99.6 |
| Embodiment 13 | ??0.5 | ??22 | ??83 | ??99.6 |
| Embodiment 14 | ??0.2 | ??35 | ??95 | ??98.3 |
| Embodiment 15 | ??0.5 | ??29 | ??86 | ??99.8 |
| Embodiment 16 | ??0.5 | ??14 | ??75 | ??99.5 |
| Embodiment 17 | ??0.5 | ??20 | ??85 | ??99.7 |
| Embodiment 18 | ??0.5 | ??23 | ??81 | ??99.8 |
| Embodiment 19 | ??3.6 | ??30 | ??88 | ??100 |
| Embodiment 20 | ??0.5 | ??15 | ??79 | ??99.3 |
| Embodiment 21 | ??0.5 | ??23 | ??84 | ??99.6 |
| Embodiment 22 | ??0.5 | ??26 | ??88 | ??99.7 |
| Embodiment 23 | ??0.5 | ??32 | ??90 | ??99.8 |
| Embodiment 24 | ??0.5 | ??13 | ??70 | ??99.1 |
| Embodiment 25 | ??0.5 | ??15 | ??73 | ??99.2 |
| Embodiment 26 | ??0.5 | ??18 | ??80 | ??99.3 |
| Embodiment 27 | ??0.5 | ??28 | ??88 | ??99.9 |
| Embodiment 28 | ??0.5 | ??10 | ??69 | ??89.3 |
| Embodiment 29 | ??0.5 | ??12 | ??72 | ??90.4 |
| Embodiment 30 | ??0.5 | ??16 | ??80 | ??99.5 |
| Embodiment 31 | ??0.5 | ??26 | ??87 | ??99.8 |
| Embodiment 32 | ??0.5 | ??35 | ??91 | ??99.9 |
| Embodiment 33 | ??0.5 | ??39 | ??97 | ??100 |
| Embodiment 34 | ??0.5 | ??38 | ??94 | ??100 |
| Embodiment 35 | ??0.5 | ??29 | ??89 | ??99.9 |
| Embodiment 36 | ??0.5 | ??30 | ??91 | ??99.9 |
| Embodiment 37 | ??0.5 | ??31 | ??92 | ??99.9 |
| Comparative example | ??0.5 | ??3 | ??50 | ??65.6 |
Claims (10)
1, a kind of Preparation of catalysts method that is used for refining crude terephthalic acid, catalyzer is a carrier with particle or pressed active carbon, supported active component metal Pd, the content of metal Pd is 0.2～4wt% in the catalyzer, this preparation method may further comprise the steps successively:
1) carrier active carbon carries out pickling, and the acid concentration of pickle solution is 0.1～5N, and a kind of in hydrochloric acid, nitric acid or the phosphoric acid taken from acid;
2) carrier active carbon is washed with water to neutrality;
3) carrier active carbon is with halogen-containing ionic solution immersion, and the halogen ion concentration of infiltrate is 0.01～0.5N, and the infiltrate consumption is 0.1～3.0 times of gac saturated extent of adsorption, and infiltrating time is 2～24 hours;
4) the drying support gac is removed moisture;
5) be mixed with Pd solution with the water-soluble Pd of containing compound and a kind of complexing agent and water, with Pd solution impregnation or sprinkling carrier active carbon, make and contain that Pd is compound loaded to obtain catalyst precursor in gac, the content that contains the Pd compound in the Pd solution is counted 15～20wt% with Pd, the mol ratio of complexing agent and Pd is (0.01～1): 1, complexing agent is taken from oxine, 2,3, any in 4-trihydroxy--4-sulfonic acid nitrogen benzide, phenanthroline, Ortho-Aminophenol, salicylic acid sodium or the salicylaldhyde oxime;
6) catalyst precursor reduces processing with reductive agent after aging, makes divalence Pd in the Pd compound be reduced to metal Pd and promptly gets catalyst prod.
2, Preparation of catalysts method according to claim 1 is characterized in that the halide-ions described in the step 3 is Br
-1Or I
-1
3, Preparation of catalysts method according to claim 1 and 2 is characterized in that the halide-ions described in the step 3 is from alkali-metal halogenide.
4, Preparation of catalysts method according to claim 3 is characterized in that described alkali-metal halogenide is the halogenide of potassium.
5, Preparation of catalysts method according to claim 1 is characterized in that the described complexing agent of step 5 is an oxine, 2,3,4-trihydroxy--4-sulfonic acid nitrogen benzide or phenanthroline.
6, Preparation of catalysts method according to claim 1 or 5 is characterized in that the mol ratio of described complexing agent of step 5 and Pd is (0.05～0.6): 1.
7, Preparation of catalysts method according to claim 1 is characterized in that the described Pd of the containing compound of step 5 takes from any in the title complex of the subsalt of the halogenide of Pd, acetate, nitrate, the acid of chlorine palladium, the acid of chlorine palladium or palladium ammonia.
8, Preparation of catalysts method according to claim 7 is characterized in that the described Pd of containing compound is acid of chlorine palladium or palladium.
9, Preparation of catalysts method according to claim 1 is characterized in that the described reductive agent of step 6 takes from any in formic acid, sodium formiate, formaldehyde, hydrazine hydrate, glucose or the hydrogen.
10, Preparation of catalysts method according to claim 9 is characterized in that described reductive agent is a sodium formiate.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104549239A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Crude terephthalic acid hydrofining catalyst |
| CN104549240A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Crude terephthalic acid hydrofining catalyst and preparation method thereof |
| CN113600181A (en) * | 2021-06-30 | 2021-11-05 | 中海油天津化工研究设计院有限公司 | Preparation method of nano palladium supported catalyst |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4394299A (en) * | 1981-10-29 | 1983-07-19 | Standard Oil Company (Indiana) | Palladium-rhodium catalyst for purification of crude terephthalic acid |
| US4791226A (en) * | 1983-06-23 | 1988-12-13 | Amoco Corporation | Catalyst and process for purification of crude terephthalic acid |
| ITMI971161A1 (en) * | 1997-05-19 | 1998-11-19 | Montecatini Tecnologie Srl | HYDROGENATION CATALYSTS |
| CN1213803C (en) * | 2002-05-16 | 2005-08-10 | 中国石化上海石油化工股份有限公司 | Hydrogenating catalyst for refining terephthalic acid |
-
2004
- 2004-06-18 CN CNB2004100252668A patent/CN100402144C/en active Active
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104549239A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Crude terephthalic acid hydrofining catalyst |
| CN104549240A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Crude terephthalic acid hydrofining catalyst and preparation method thereof |
| CN104549239B (en) * | 2013-10-28 | 2017-04-12 | 中国石油化工股份有限公司 | Crude terephthalic acid hydrofining catalyst |
| CN104549240B (en) * | 2013-10-28 | 2018-01-09 | 中国石油化工股份有限公司 | Hydrofining crude terephthalic acid catalyst and preparation method thereof |
| CN113600181A (en) * | 2021-06-30 | 2021-11-05 | 中海油天津化工研究设计院有限公司 | Preparation method of nano palladium supported catalyst |
| CN113600181B (en) * | 2021-06-30 | 2023-08-04 | 中海油天津化工研究设计院有限公司 | Preparation method of nano palladium supported catalyst |
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| Publication number | Publication date |
|---|---|
| CN100402144C (en) | 2008-07-16 |
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